Process of making beryllium hydroxid.



sTA'T s PATENT .GFFTGE.

FRITZ HABER AND GABRIEL VAN OORDT, OF KARLSRUHE, AND FRIEDRICH BEAN, OF MANNHEIM, GERMANY.

-PROCESS OF MAKING BERYLLIUM HYDRDXlD- To all whom it may concern:

Beit known that we, FRITZ HABER and GABRIEL VAN OORDT, residing at Karlsruhe,

and FRIEDRICH BRAN, residing at Mannheim, in the Grand Duchy of Baden, Empire. of Germany, sub'ects of the German Em eror, have invente ium Hydroxid, of which the following is a specification.

Our invention relates to the separation of beryllium compounds, such as the hydroxids from mixtures of such compounds as found, for example, in minerals. x v The object of the invention is to provide a method of obtaining the beryllium compounds, and in particular beryllium hydroxid, by an economical and commercially available manner.

With these objects in view our invention consists in the methods, steps, and features 9 now to be described, and to be pointed out in I the claims.

Although the behavior of the beryllium hydroxid with respect to alkalies and acids has often been the subject of.experiment since the discovery of the metal by Vauquelin, the .qualities of beryllium hydroxid, which are described in this specification and which are to be'em loyed for separating beryllium hydroxid om other hydroxids, especially from those of iron andaluminium, have remained unknown.

The discoverer of beryllium, Vauquelin, (An/n. Oh'im. Phys. I, 26, 1 798,dp. 155 and 170) characterizes beryllium hy oxid as a substance which is less easily dissolved in caustic potash than alumina, (Al O- Graf Schaifgotsch and C. G. Gmelin '(Pogg. Ann. 50, 1840, pp. 175 and 185) discovered independently' that when the hydroxid is dis solved in strong caustic potash and the solution is then diluted said hydroxid is precipitated by heating. C. G. Gmelin says that this property of beryllium hydroxid is not shared by alumina and pro oses to utilize this quality for separating oth earths by dissolving them together in strong caustic potash and then diluting and boiling the solution. This su gestion of Gmelin'has been characterize as impracticable by Weeren (Pogg. Ann. 92,1854, p. 91) both for analytical and technical purposes, be-

cause the latter found by ex eriment that at times more than three-fourt s of the beryllia I Specification of Letters Patent. Application filed March 8,1904. Berial No. 197,199.

certain new and usefu Im-. rovements in the Manufacture of Beryl- Patented June 5, 1906.

remains in 3, 34, 1855, p. 5) likewise condemns process as technically-impracticable.

solution. Debray (Ann. Ohim.

Hof-

meister (Journal pr. Chem. 76, 1859, p. 3)

and Joy (Journal pr. Chem, 92, 1869, p. 230) likewise found this method of separation impracticable. Zimmermann (Dissertation, Berlin, 1887) worked with caustic potash and caustic soda according to the suggestion of Gmelin and found that'caustic soda is not to be recommended for the separation of the beryllium compound. (Zimmermann lost the.

seven per cent-of the beryllia.) With caustic otashhe could obtain a se aration only un er such conditions as'exc uded all use on a larger scale. His method being characterized as highly unreliable and the conditions and steps of the same being insufiiciently described, it cannot even be re eated on a small scale. (He dissolved ony one am of the mixed hydroxids per liter. He says that by diluting the solution to double the extent fifty-eight per cent. of the alumina was 'recipitatetd. The concentration of the alk i isnot iven at all.)

Penford and arper (Classen, Ausgewiihlte Methodn' I, Braunschweig, 1901, p.

717) desired to effect the separation by dissolvin the earths in very concentrated caustic so a, dilutingthe solution to eight hundred cubic centimeters and boiling. This method also istechnically impracticable and cannot be repeated with certainty of success. This is made all the more evident through a statement of Hantzsoh, (Zeitschriyt f. Anorg. Chem. 30, 1902., p. 338,) who says that a sooxid to eight molecules of caustic soda gives a precipitate which is always far from com lete.

Gmelins method above described t erefore appears to be impracticable according to the statements of subsequent investigators lution containing one .molecule of beryllium and has been criticized on this score by authors of texflbook-for example, by Graham- Otto and Treadwell.

The proposed method of Gmelin is based IOO' entirely on the observation that beryllia is.

precipitated if its diluted solution in caustic alkali is boiled. Of the precipitated beryllia Gmelin states that it dissolves with difficulty in dilute caustic potash, but very readily in acids, and that the particular form which dissolves in a dilute solution of caustic potash with difliculty can only be produced in this way. 1

Our researches and investigations in this direction have given the following surprising results: First, that the particular form of beryllia, or rather beryllium hydroxid, which has taken place; second, that both forms'of the precipitated beryllium hydroxid by heat- 'ing with a small quantity of caustic potash quite insufficient -ior dissolving it are converted into this new form, which is almost insoluble or dissolves with difiiculty in acids at ordinary temperatures; third, that other I forms also difficult of solution result if a mixture-of beryllia andother oxids,such as alumina inthe form of hydroxids, is treated with a quantity of caustic soda (in suitable concentration) sufficient to dissolve the alumina, but not the 'beryllia; fourth, that the forms of beryllium hydroxid practically-insoluble in "alkali may also be produced by treating beryllium hydroxid at'ordinary or at higher temperatures by boiling with pure water or with water containing ammonia, carbonates of alkali,"'.or. even indifferent substances, which has been expressly denied by C. G. Gmelin; fifth, finally it was found thatthe treatment with water, steam, or solutions as above may be replaced by mere drying.

Thus, for instance, it was found for the solubility of a beryllium hydroxid which had been dried for eight days at ordinary temperature that at from 20 to 23 centigrade there would dissolve in a half-normal, a normal, or a double-normal solution of NaOH, respectively, sixty, one .hundred and seventy, or five hundred and seventy milligrams per liter, andat 100 centigrade these solubilities were found to be, respectively, eighty, two hundredan'd ninety, or one thousand and twenty milligrams per liter. On the other hand, for alumina Iwhich'had stood for more than one year at ordinary temperature these solubilities for the same solutions and temperatures were found to be respectively, 11.26, 11.39, 14.4, 11.25, 20.3, or

44.4 grams per liter. 7 This is expressed in a more perspicuous form in the following table:

I I BeO. "Temperature NaHO solution.

in n/2. l n. 211. I

20 -23 0 mg. 170 mg. 570 m per liter. 100 (J 80 mg. 290 mg. 1, 020 mg. per liter.

soar-2s c 9.26 g 11.39 14.4 g. a liter.

100 C 11.25g 20.3 g. 44.4 g. periiter.

' Furthermore, it has been found for the ,solubility of beryllium hydroxid, which has been heated during five hours in pure water at 100 centigrade, that fifty-two milligrams were soluble in one liter of half-normal caustic-soda solution. In the case of the use of water containing ammonia substantially'the same values were obtained under similar conditions. I J

On the other hand, if alumina is heated for the same time with a quantity of half-normal caustic-soda solution, insufiicient for soa lution, of the alumina, the remainin ,part

may be dissolved in a new quantity 0 caustic soda as easily as if that treatment had not preceded. I

The beryllium hydroxid undergoes an al teration under the influence of time, whereby from the well-known form which readily dissolves in dilute alkali solutions in solutions of carbonates of potassium of sodium and 'of, ammonium. and acids aged. forms arise which are insoluble, or only soluble with difficulty not only in alkalies, but also in acids. The increase in temperature and also the addition of caustic potash and caustic soda and the like exert an accelerating in fluence on this ageing effect.

Aluminium hydrate, ferric hydrate, and some other hydroxids also possess the property of chan ing to an aged form, as Berthalot (AW/1.0 t'm. Phys. 5, 4 vol. p. 174) and Hantzsch (Zeitschrift f. Anorg. Chem. 30, 1902, p. 38) have observed, but'neither to the same extent nor under the same condi tions as the beryllium hydroxid. In order toemphasize the great differences between fresh and aged forms of hydroxids,- the solubilitis for freshly-precipitated beryllium hydroxid at the ordinary temperature in caustic soda of different degrees of concentration will now be given, these particulars having been partly communicated by Rubenbauer (Zeitschrtft f. Anorg. Chem. 30,1902,

p. 331) and having in part been ascertained by our own researches.

Our invention utilizes the newly-discow i ered facts above setforth, and one feature of the same accordingly1 consists in heating un-- dissolvedberyllium ydr'oxid either alone or in an aqueous bath which may be simply wa rro ter or a solution of caustic alkali, including ammonia, or of alkali carbonates.

'Afurther feature of our invention involves the treatment of mixtures containing beryllium oxid after having been thus reacted on with acids to separate the acid from the beryllium hydroxid which has become almost insoluble or soluble with difliculty in the acid.

A number of examples showing the preferred manner of proceeding under our invention will now be given.

Example 1: A mixture of hydrates of beryllium, aluminium, and iron is heated in so much diluted (for instance, n/Z) caustic soda as is necessary to dissolve the alumina. If, for instance,thirteen grams BeO inthe form of beryllium hydroxid, seventeen grams A1 0 in the form of aluminium 'hydroxid, one gram Fe O in the form of ferric h drate are mixed together, this mixture is eated with 1.5 to 1.6 liters of half-normal caustic soda for one or two hours. Hereby at the most 0.1 gram BeO is dissolved in the form of Be(HO),-that is to say, 0.75 per cent. of the existin berylliawhereas the alumina is completeIy eliminated. The remainder of the beryllium hydroxid is now present in a form which is difficult to dissolve and is freed from iron by simply washing it with acidfor dinstance, with warm dilute hydrochloric aci Example 2: Instead of heating the mixed hydroxids with alkali they may be heated in an aqueous baththat is to say, with water-with an aqueous.solution of ammonia or with a solution of soda or of carbonate of potassium, with or without indifferent substances added to such liquids or solution. The heating with water may be carried out, for instance, in such a manner that the mixture of hydroxids set forth in Example 1 is treated in damp condition with water or steam of 100 centigrade or at a somewhat higher temperature for about five hours. The beryllium hydroxid thereby becomes almost completely insoluble in alkali, as seen from the above table of solubilities. If then the mixture is treated with so much dilute (for instance, half-normal) caustic soda, as is necessary for dissolving the aluniina according to the above-mentioned example, the alumina is extracted from the mixture by being dissolved. If this extraction of alumina is carried out at higher temperatures sufficient to cause the caustic alkali simultaneously to change the beryllium compound into the aged form, as above shown, the iron may then be eliminated by means of acid, as mentioned in the preceding example. If it is desired to affect the extraction in the cold and then to eliminate the iron by means of acid, it may be necessary to continue for a longer period the preceding treatment with steam or hot water in order that by this treatment the condition in which it is difiicult to dissolve the beryllia in acid may be perfectly obtained.

the compounds soluble in' immediately pure in Example 3 The process is the same as that in Example 2, with the exception that the treatment with water, steam, or solution is replaced by a drying process carried out at ordinar or highertemperatures.

In al these processes the presence of such hydroxids as will remain easily soluble in diluted alkali or in acid is permissible. I

To apply this process to beryl or similar minerals containing beryllium, the solution obtained during the process-for example, a solution of acid salts of alumina, of beryllia, and of iron-is mixed with so much caustic alkali that only the alumina is held in solution, and then the process is carried out according to the directions given under Example 1, or caustic alkali or soda is added to such solution only up to the point of neutralization and the process is then carried out according to Examples 1, 2, or 3. If, however, an alkaline-fused mass or an alkaline solution is to be treated, the process may be so carried out that the uantity and the degree of concentration 0? the alkali fulfil the conditions of Example 1, whereupon we proceed according to said Example 1. In the case of weaker alkalinity we follow eitherExample 1, 2, or 3.

As compared with Gmelins process referred to above, our invention offers the im portant advantage that the aluminate solution may be regenerated without evaporation by a simple treatment with chalk after the precipitation of the alumina by means of carbonic .dioxid. When obtained in this manner, the berryllium hydroxid often contains small quantities of ferric hydrate and alumina. In order to eliminate these, We proceed in the following manner As Lacombe (00m tes Rendus, vol. 133, p. 874-, 1901) has found beryllia readily forms compounds with simple fatty acids, which are soluble in chloroform. Our experiments in this connection have proved that this quality may be utilized for the separation of the bcryllia from alumina and iron. For this ITO purpose the compounds which are to be separated are transformed into acetates, treated with glacial acetic acid and extracted b chloroform, whereby perfectly-pure b'ery lium acetate is obtained, which may be utilized for the manufacture of other beryllium compounds. If, for instance, there are to ten parts of BeO (in form of Be (OHM one part of A1 0 and of Fe O (in the form of the h droxids,) they are dissolved in acetic acid of any concentration. evaporated and stirred up with glacial acetic acid, heated until dry, the atmospheric humidity being excluded (by distilling oif the glacial acetic acid) and extracted with chloroform. In driving off the chloroform ninety per cent. of the employed BeO are obtained the form of crystallized compounds of the acetic acid. By means of The liquid is then' 2. second treatment with glacial acetic acid and chloroform the quantity of the beryllia obtained in apure form is easily brought up to ninety-five per cent. The yield becomes still greater if the original material is poorer in alumina and iron. Instead of extracting the acetates by means of chloroform immediately after the treatment with glacial acetic acid water may first be added, which dissolves the acetate of iron and aluminium, but does not dissolve the acetate of beryllium, and then the extraction by means of chloroform may take place.

hat we claim is I. The process of rendering beryllium hydroxid insoluble or soluble with difficulty not only in alkali but also in acids, which consists in heating beryllium hydroxid while in an undissolved condition.

2'. The process of rendering beryllium hydroxid insoluble or soluble with difficulty not only in alkali but also in acids, which consists in heating beryllium hydroxid while in in lfilldlSSOlVGd condition and in an aqueous 3. The process of rendering beryllium hydroxid insoluble or soluble with difliculty not only in alkali but also in acids, which consists in heating beryllium hydroxid while in an undissolved condition in the presence of an alkaline solution.

4. The process of rendering ber llium hydroxid insoluble or soluble with di culty not only in alkali but also in acids, which consists in heating beryllium hydroxid while in an undissolved condition and in the presence of an alkali-earbonate solution.

5. The process of separating beryllium hydroxid from aluminium hydroxid which consists in heating a mixture containing beryllia and alumina while in an undissolved condition and then treating the mixture with an alkali-bath just sufficient to dissolve the alumina.

6. The process of separating beryllia from alumina, which consist-s in heating a mixture containing beryllia and alumina in an aqueous bath while in an undissolved condition and then treating the mixture with an alkalibath just sufiicient to dissolve the aluminium compound.

7. The process of separating beryllia from alumina, which consists in heating a mixture containing beryllia and alumina in the presence of an alkaline solution and while in an undissolved condition and then heating the mixture in an alkali-bath just suflicient to dissolve the aluminium compound.

8. The process of separating the hydroxids of beryllium and aluminium which consists in heating a mixture containing the two in the presence of an alkali-carbonate solution While in an undissolved condition and then heating the mixture in an alkali-bath just suflicient to dissolve the aluminium compound.

9. The process of separating the hydroxids of beryllium, aluminium and iron which consists in first heating the mixture of or containing these compounds while the beryllium hydroxid is in an undissolved condition and then heating the said mixture in dilute alkali just suiiicient to dissolve the aluminium compound and then treating the undissolved residuum with acid to dissolve out the iron compound.

10. The process of separating beryllium hydroxid from iron hydroxid which consists in rendering the beryllium hydroxid insoluble or soluble with diflieulty in acids by heating a mixture containing beryllium and iron hydroxid in the presence of an alkali solution and in an undissolved condition and then treating the mixture with acid for dissolving the iron compound.

11. The process of. separating beryllium hydroxid from aluminium and iron hydroxids which consists in rendering the beryllium hydroxid insoluble in acids by heating the mixture of beryllium, aluminium and iron hydroxid in the presence of an alkali solution which is just suflicient to dissolve the aluminium compound and then treating the undissolved residuum with acid for dissolving the ironhydroxid. N

12. The process of separating beryllium hydroxid from aluminium and iron hydroxid which consists in rendering the beryllium hydroxid insoluble in acids by heating the mixture of beryllium, aluminium and iron hydroxid in an aqueous bath while the beryllium hydroxid is undissolved and then in alkali' solution just sufiicient to dissolve the aluminium hydroxid andthen treating the undissolved residuum with acid for dissolving the iron hydroxid.

13. The process of separating beryllium, aluminium and iron hydroxids which consists in heating a mixture of or containing these compounds while the beryllium com pound is undissolved, in the presence of an alkali-carbonate bath, then heating the said mixture in alkali. solution just sufiicient to dissolve the aluminium compound and treating the undissolved residuum with acid to dissolve the iron compound.

14. The process of obtaining purified beryllium hydroxid from material containing the hydroxids of beryllium, aluminium and iron, which consists in first heating the mixture of or containing these compounds while the beryllium hydroxid is in an undissolved condition, then heating the said mixture in dilute alkali just sufiicient to dissolve the aluminium compound, then treating the undissolved residuum with acid to dissolve out the iron compound, and purifying the resultant beryllium hydroxid as an acetate.

15., The rocess of obtaining purified be- I ryllium hy oxid from material containjn the hydroxids of beryllium, aluminium and ir'on,'which consistsin first heating the mate rial While the beryllium hydroXid is in an undissolved condition, then heating said mixture in dilute alkali just sufiicient to dissolve the aluminium compound, then treating the undissolved residuum with acid to dissolve out the iron compound, separating the beryl lium hydroxid, dissolving it in acetic acid, evaporating the solution, treating it with glacial acetic acid and finally extracting the I same with chloroform.

In testimony whereof We have signed this I 5 specification in the presence of two subscribing Witnesses.

FRITZ HABER. GABRIEL VAN OORDT. FRIEDRICH BRAN. I

Witnesses:

H. W. HARRIs, J AGOB ADRIAN. 

